Blue-sulfur dye and process of making same.



I NITED STATES Patented May 16, 1905.

PATENT OFFICE.

JULIUS ABEL, OE MANNHEIM, AND ARTHUR LUTTRINGHAUS, OF LUD- WVIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIGNORS TO BADISOI-IE ANI- LIN & SODA FABRIK, OF LUDVVIGSHAFEN-ON-THE-RHINE, GERMANY,

A CORPORATION OF BADEN.

BLUE-SULFUR DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 790,167, dated May 16 1905.

Application filed February 21, 1905. Serial No. 246,766.

To all whmn it may concern.-

Be it known that we, JULrUs ABEL, doctor of philosophy and chemist, a citizen of the free Hausa town of Hamburg, residing at Mannheim, in the Grand Duchy of Baden, and ARTHUR LUTTRINGI-IAUS, doctor of philosophy and chemist, a subject of the King of Prussia, German Emperor, residing at Ludwigshafen-on-the-Rhine, in the Kingdom of Bavaria, Grcrman'Empire, have invented new and useful Improvements in Sulfur Coloring-Matters and Processes of Making the Same, of which the following is a specification.

Our invention relates to the production of I 5 new blue to violet-blue coloring-matters containing sulfur.

We have discovered that by heating an alkali salt of a para-amido-parm-hydroxydiarylamin body with sulfur new and valuable col- 2o oring-matters containing sulfur are obtained which possess the peculiar characteristic that .theyare difficultly soluble in sodium-sulfid solution in the cold, while in a hot solution they are more readily soluble; but in both '25 cases the solution obtained is almost colorless or possesses only a faint yellow color and no intermediate formation of a blue solution its para-arylamido derivative n (p H 10) and the homologues and substitution products of these compounds. The coloring-matter In the cold solution the fiber has essen' which we desire to claim specifically is that obtainable by heating the alkali salt of para- 5 phenylamido paral hydroxydiphenylamin with sulfunand this produces pure-blue shades on vegetable fiber.

The following examples will serve to further illustrate the nature of our invention, which, however, is not confined to these examples. The parts are by weight.

Example 1: Introduce twenty-seven and six-tenths (27.6) parts of para-phenylamidoparal-hydroxydiphenylamin into a solution of four (at) parts of caustic soda in ten (10) parts of water, which is contained in an open vessel provided with a stirring apparatus and which is heated in an oil-bath, the temperature of which should be about one hundred and sixty-five degrees centigrade, (165 O.) As soon as the excess of water has distilled ofi add twenty and a half (20.5) parts of sulfur to the mass and raise the temperature slowly. When an internal temperature of about one hundred and thirty-five degrees centigrade (155 O.) is reached, the whole melts and reaction takes place' while frothing considerably. Allow the temperature to rise to about one hundred and fifty degrees centigrade C. )until the frothing ceases. Then heat the product obtained ina drying-oven for about four (4:) hours at a temperature of about one hundred and sixty-five degrees centigrade O.) and then for another two (2) to three (3) hours at a temperature of one hundred and seventy-five degrees centigrade, G.) Then mix the dried product with seven and one-tenth (7.1) parts of sulfur and heat for another two (2) hours at a temperature of from one hundred and eighty to one hundred and eighty-five degrees centigrade, (18O O.) Dissolve the product so ob- I tained in a solution of seventy-five (75) parts of sodium sulfid in a large quantity of hot 9 water to which preferably a'little caustic soda is added. Filter the solution and then blow air through the filtrate while maintaining this at a temperature of about sixty degrees centigrade, (60 O.) The coloring-matter sep- 95 arates out as a powder with metallic luster and should be filtered off and well washed with hot water. It is slowly soluble in hot sodium-sulfid solution, yielding a pale-yellow solution which dies vegetable fiber shades which on exposure to air become pure blue. The coloring-matter is practically insoluble in cold anilin and is only slightly soluble in hot anilin, yielding a blue solution. It is easily soluble-in concentrated sulfuric acid, the solution being blue.

Example 2: Introduce twenty-six and nine tenths (26.9) parts of dry para-amido-parmhydroxy meta1- metal dichlordiphenylamin into a solution of four (4:) parts of caustic soda in ten (10) parts of water contained in a vessel which is heated in an oil-bath, the temperature of the bath being from one hundred and sixty to one hundred and sixty-five degrees centigrade, (160 165 C.) After a short time add eighteen and a half (18.5) parts of sulfur and maintain the temperature of the mixture for from four (4) to five (5) hours between one hundred and forty and one hundred and forty-two degrees Centigrade, (140 -142 G.) Then dissolve the melt in a hot dilute solution of sixty parts of sodium sulfid, to which conveniently a little caustic soda has been added, and then blow air through the hot solution and filter off the precipitated coloring-matter while hot and wash well with hot water. The coloring-matter when dryis a powder with coppery luster, which is diflicultly soluble in cold sodium-sulfid solution, but which is more soluble on warming, and in both cases a colorless or only pale-yellowcolored solution is obtained, upon which at the surface exposed to the air the coloring,- matter immediately separates as a skin. The coloring-matter dyes vegetable fiber from a hot sodium-sulfid bath, producing violet-blue shades.

Example 3: Introduce twenty-three (23) parts of para-amido-xylyl-paral-hydroxy-diphenylamin into a solution of four (4) parts of caustic soda and ten (10) parts of water, as described in the foregoing Example 2. As soon as the mixture has become viscous add eighteen (18) parts of sulfur, and after a short time a homogeneous melt is formed which evolves sulfureted hydrogen and which grad ually becomes viscous. As soon as the temperature has reached one hundred and forty degrees centigrade (hi0 (3.) place the melt in a drying-oven and heat for from four (4) to six (6) hours at a temperature of between one hundred and sixty-five and one hundred and seventy degrees centigrade, (165 470 C.)

Then dissolve the product in a boiling solution of sixty (60) parts of sodium sulfid and fifteen (15) parts of caustic soda in one thousand (1,000) parts of water. Filter the solution while hot and then blow air through the filtrate while maintaining this latter at a temperature of sixtydegrces centigrade, (60 C.) The coloring-matter separates out as a powder with a coppery glance. Filter this 011' and press and then wash well with boiling water, and, finally, dryit at a fairly high temperature. The coloring-matter is diliicultly soluble in cold sodium-sulfid solution; buton warming it is more quickly soluble, yielding a pale-yellow solution which dyes unmordanted fiber violet-blue shades.

Now what we claim is- 1. The process for the production of blue to violet-blue coloring-matters containing sulfur, by heating an alkali salt of a para-amideparal-lnvdroxydiarylamin body with sulfur.

2. The process for the production of a blue coloring-matter containing sulfur, by heating an alkali-salt of para-phenyl-amido-parai-hydroxydiphenylamin with sulfur.

3. As new articles of manufacture, the coloring-matters which can be obtained by heatingwithsulfur an alkali salt of a para-amideparal-hydroxydiarylamin body, which coloring-matters contain sulfur and which are soluble in hot sodium-sulfid solution yielding paleyellow solutions without the intermediate formation of a blue solution, from which vegetable fiber takes up a leuco compound which on exposure to the air becomes blue to violetblue.

4. As a new article of manufacture, thccoloring-matter which can be obtained by heating with sulfur an alkali salt of 1')araphenylamido-parm-h yd roxydiphen ylam in, wh ichcoloring-matter contains sulfur, and which is with difficulty soluble in cold sodium-sullid solution, but more quickly soluble in hot sodium-sulfid solution, yielding a pale-yellow solution without the intermediate formation of a blue solution, and from the hot solution vegetable fiber takes up a leuco compound, which on exposure to the air becomes pure blue.

in testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

JULIUS ABEL. ARTHUR LUTlRl NG-lrl A U S.

Vitnesses:

ERNEST F. Ennn'Aun'r, Jos. H. LuUTn. 

